CN1324716A - Method for treatment of fire retardant resin composition - Google Patents
Method for treatment of fire retardant resin composition Download PDFInfo
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- CN1324716A CN1324716A CN01116994A CN01116994A CN1324716A CN 1324716 A CN1324716 A CN 1324716A CN 01116994 A CN01116994 A CN 01116994A CN 01116994 A CN01116994 A CN 01116994A CN 1324716 A CN1324716 A CN 1324716A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/06—Recovery or working-up of waste materials of polymers without chemical reactions
- C08J11/08—Recovery or working-up of waste materials of polymers without chemical reactions using selective solvents for polymer components
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
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Abstract
For efficiently recycling a flame retardant resin composition constituted of a flame retardant and a resin, the present invention provides a method for treating a flame retardant resin composition comprising a step of bringing at least part of a flame retardant resin composition containing a resin and a flame retardant into contact with a pressurized fluid constituted of a solvent to reduce the flame retardancy.
Description
The processing method that the present invention relates to from resin combination, to remove the fire retardant composition with containing the technology of the resin combination of fire retardant, relating to and resin is become be easy to utilize again as renewable resource utilization.
Specifically, remove the fire retardant composition in the resin combination that contains halogen containing flame-retardant that the present invention relates to from the display housing of for example television set, computer etc., use, the processing method that makes residual resin become and be easy to utilize again.
In recent years, people wish to effectively utilize resource, and various raw-material resource regeneration technology are developed.Resinogen materials such as plastics are mainly discarded by means such as burning and landfills usually, we can say that therefore the waste recycle that produces after reaching goods in the production of articles operation uses is very important.As this reutilization technology, at present positive broad research is burned resin to obtain fuel and effectively to utilize the heat of its combustion heat to utilize method again, make resin oiling or gasification utilize method again, resin is decomposed make it utilize method and the direct Reuse of materials method that the resin granulation is re-used etc. again with the chemistry as the oligomer of resin raw material and monomeric form regeneration with the chemistry that obtains raw material or fuel.In these reutilization technologies, the difficulty or ease of processing method, and the quality of gained raw material and fuel is considered to very important.
Usually, consider security, the resin that uses in casing of domestic electrical equipment and the substrate etc. contains fire retardant and therefore has anti-flammability.For example at present as the shell of the display of television set and computer and video recorder etc., the high-impact polystyrene resin thermoplastic resins such as (polybutadiene and blends of polystyrene etc.) that generally uses styrene resin, ABS (acrylonitrile-butadiene-styrene (ABS)) resin, has the resistance to impact of improvement.
Yet the existence of thermoplastic resin alicyclic monomer has highly flammable problem.Therefore the angle that burning spreads when preventing fire is admixed the fire retardant resin composition with anti-flammability thereby be extensive use of with anti-flammability reagent such as fire retardant and flame retardant and resin.Particularly halogen containing flame-retardant can make various thermoplastic resins produce high flame retardancy effectively, and cheap, therefore worldwide extensively adopts.
When these fire retardant resin compositions are utilized again,, in addition,, cause the quality of reconstituted product to descend because fire retardant composition or its analyte are sneaked into because the existence of fire retardant composition as generating raw material and fuel, is handled comparatively difficulty.Therefore, particularly to the processing of the resin combination that contains fire retardant with utilize again and do not do what effort basically, become a big problem.
For this reason, for example as fire retardant resin composition utilize method again, studied by heat and utilized again or chemistry utilizes etc. again and to make resin in the method that contains pyrolysis under the state of fire retardant.The open communique of Japan's special permission discloses a kind of 1999 No. 140223 with the heating of plastics such as polyvinyl chloride, has removed halogenic ingredient, the method that resin is decomposed.The open communique of Japan's special permission then discloses a kind of method that resin is decomposed with fire retardant 1999 No. 228731.
But when the fire retardant that uses is halogen containing flame-retardant, utilizes in heat again and to utilize with chemistry again, halogenic ingredient contained during pyrolysis can break away from, and emits halogen compounds such as halogen gas and hydrogen halides.And in burning is handled, may produce harmful halogen compounds such as bioxin.These halogen compounds easily cause the equipment corrosion in the treatment process, and, be discharged in the atmosphere in order not to be harmful to halogen compounds, also need enough equipments.
For preventing container corrosion etc., when plastics such as resolution process polyvinyl chloride and polyvinylidene chloride, studied and carried out the method that dehalogenation is handled in advance.For example the open communique of Japan special permission disclose for 1999 No. 116729 a kind of with plastics heat treatment dehydrochlorination in organic solvent, the method that low boiling point component that hydrogen chloride produces with decomposing plastics etc. is removed.The open communique of Japan special permission then discloses the method that a kind of halogen of sloughing during with heating of plastic reclaims, residual plastics decomposed with supercritical fluid for 1999 No. 140223.In addition, the open communique of Japan special permission discloses for 1999 No. 156378 a kind of when producing harmful halogen compounds such as De bioxin carrying out overcritical hydroxylating resolution process when burning is handled, and mixes the method for nertralizer with the halogen neutralization.
Yet in the past, as the processing method that fire retardant resin composition utilizes again, being mostly of research utilized method again with the chemistry that resin decomposes, and the processing method of Reuse of materials is less studied.Utilize required energy again and material utilized to reduce again, therefore, its technological development is very important.For example, utilize again by chemistry resin is decomposed when obtaining its raw material, need the required energy of further synthetic resin, and if, just needn't drop into such energy probably to Reuse of materials.
In the processing method of in the past the resin combination that contains halogenic ingredient, the required heat treatment of dehalogenation must be arranged, and because heating, the color of resin itself can change, molecular weight can reduce, also can be crosslinked and deterioration.Though the therefore purposes utilized again of the chemistry that is suitable for decomposing of the resin through handling like this, its quality is difficult to be fit to Reuse of materials, that is, utilize as resin again.That is to say,,, then need to develop the technology that improves the reconstituted product quality for Reuse of materials though for the chemistry that carries out pyrolysis utilizes again, there is not such problem.
The problems referred to above that exist before considering, the objective of the invention is to, the anti-flammability way to solve the problem of the fire retardant resin composition that a kind of solution is made up of fire retardant and resin is provided, and described anti-flammability problem is to hinder the principal element that fire retardant resin composition is effectively utilized again.In other words, the objective of the invention is to, a kind of like this processing method of fire retardant resin composition is provided, and this method can be removed flame-retardant composition from fire retardant resin composition, and the having of situations such as the deterioration that obtains can not occurring being heated is fit to the resin of the quality utilized again.
The present invention also aims to provide a kind of on the basis that fire retardant is removed from the resin combination that contains fire retardant, suppress regenerating resin and descend, and make its reprocessing easy processing method that becomes by the quality that the deterioration of being heated etc. causes.That is, specifically, provide a kind of and can easily with thermoplastic resin pelletizing and powder chemical industry preface make up the processing method of carrying out.
The present invention relates to a kind of processing method of fire retardant resin composition, it comprises that at least a portion that makes the fire retardant resin composition that contains resin and fire retardant and the high-pressure fluid by solvent composition contact, reduce the operation of the anti-flammability of above-mentioned fire retardant resin composition.
Specifically, this method is mainly divided following 2 kinds.
First kind of processing method is at least a portion of above-mentioned fire retardant resin composition to be contacted, by extracting the anti-flammability that above-mentioned fire retardant reduces above-mentioned fire retardant resin composition with high-pressure fluid.
In this case, above-mentioned processing method preferably comprises with the solvent that constitutes above-mentioned high-pressure fluid again and makes said extracted go out the operation of the fire retardant resin composition foaming behind the fire retardant.
In second kind of processing method, used fire retardant is a halogen containing flame-retardant, and at least a portion of above-mentioned fire retardant resin composition is contacted with high-pressure fluid, sloughs the halogen in the above-mentioned fire retardant resin composition, reduces its anti-flammability.
In this case, above-mentioned processing method preferably comprises the operation with the above-mentioned fire retardant resin composition reduction of the solvent that constitutes above-mentioned high-pressure fluid after with dehalogenation again.
In addition, preferably comprise the operation that makes the above-mentioned fire retardant resin composition foaming behind the dehalogenation with the solvent that constitutes above-mentioned high-pressure fluid again.
In the processing method of fire retardant resin composition of the present invention, above-mentioned solvent is carbon dioxide preferably.
Particularly in first kind of processing method, above-mentioned highly pressurised liquid preferably contains cosolvent.
Be preferably, the pressure of above-mentioned high-pressure fluid is more than the critical pressure of the solvent that constitutes above-mentioned high-pressure fluid and at below 3 times of above-mentioned critical pressure.
Be more preferably, the pressure of above-mentioned high-pressure fluid is in more than 1/2 and below above-mentioned critical pressure of critical pressure of the solvent that constitutes above-mentioned high-pressure fluid.
Fig. 1 is the process chart of first kind of processing method of the present invention.
Fig. 2 is another process chart of first kind of processing method of the present invention.
Fig. 3 is the structural representation that is used for the device of first kind of processing method of the present invention.
Fig. 4 is the process chart of second kind of processing method of the present invention.
Fig. 5 is another process chart of second kind of processing method of the present invention.
Fig. 6 is the another process chart of second kind of processing method of the present invention.First kind of processing method
First kind of processing method of fire retardant resin composition of the present invention at first is described, it comprises allows at least a portion of fire retardant resin composition of resinous and fire retardant contact with high-pressure fluid by solvent composition, the operation that the anti-flammability of above-mentioned fire retardant resin composition is reduced.
In first kind of processing method of fire retardant resin composition, from the resin combination that contains fire retardant, remove the fire retardant composition, and from above-mentioned resin combination, extract fire retardant with high-pressure fluid.
In first kind of processing method of fire retardant resin composition, from the resin combination that contains fire retardant, remove the fire retardant composition, it is characterized in that, aforementioned resin is a thermoplastic resin, after extracting above-mentioned fire retardant with high-pressure fluid from above-mentioned resin combination, be used in solvent used in the above-mentioned high-pressure fluid and make above-mentioned resin combination foaming.And extract resin combination behind the fire retardant, or form by the additive outside resin and the fire retardant in fact only by resin.
Applicable to the fire retardant of the present invention halogen containing flame-retardant of addition type preferably.
In the present invention, the pressure of high-pressure fluid should be in above-mentioned high-pressure fluid more than the critical pressure of used solvent, below 3 times of critical pressure.
In the present invention, used solvent carbon dioxide preferably in the high-pressure fluid.
In addition, in the present invention, good effect when containing 1 mole more than the %, 20 moles cosolvents below the %, high-pressure fluid is arranged also.
Below first kind of processing method of the present invention made more specific description.
Use the present invention, can from the resin combination that contains fire retardant, remove the fire retardant composition, obtain regenerating resin, and the quality that can not take place to cause by being heated deterioration descends.And, can under the situation that deterioration does not take place, reclaim owing to extracting as the fire retardant composition with isolated fire retardant, therefore, can utilize again it.Particularly when the resinous principle of fire retardant resin composition is thermoplastic resin, when resin is utilized again, can be easily with its pelletizing and powderization.
Can obtain the reason of these effects with Fig. 1～3 explanations below.
Fig. 1 is the process chart of first kind of processing method of the present invention.In the processing method of fire retardant resin composition of the present invention,, extract fire retardant with high-pressure fluid for from the resin combination that contains fire retardant, removing the fire retardant composition.Thus, from resin combination, isolate fire retardant, and resinous principle and fire retardant are reclaimed respectively.Resin that is recovered to like this and fire retardant have and are fit to the quality utilized again and deterioration not basically.
Fig. 3 is the structure of an example that is used for the treating apparatus of first kind of processing method of the present invention.The fire retardant resin composition 1 that will contain fire retardant joins in the high-pressure bottle 2.Pressure with constant displacement pump 6 and pressure-regulating valve 3 adjustment solvents injects this container 2 as high-pressure fluid.This solvent extracts fire retardant at high pressure conditions from fire retardant resin composition 1.When solvent under high pressure was in fluid state, it had the diffusivity of height, can soak into to resin combination inside, therefore, extracts fire retardant easily.This solvent that contains the fire retardant that is extracted sent into its pressure is descended and carry out in the separation container 4 of gas and fluid separation applications, be separated into the solvent and the fire retardant of gaseous state, from reclaiming mouthful 5 taking-up fire retardants.Recycling after the solvent cooling liquid with gaseous state.Supply with and the suitable solvent of quantity of solvent that consumes by high-pressure cylinder.Temperature during extraction can be regulated by the temperature adjustment of heat exchanger 9 or high-pressure bottle 2.
Fig. 2 is another process chart of first kind of processing method of the present invention.When the resin that constitutes fire retardant resin composition is thermoplastic resin, from resin combination, extract fire retardant with high-pressure fluid.Can obtain resin and fire retardant that its quality is suitable for utilizing again thus.The solvent that uses during again with extraction makes isolated resin expanded.By this processing, the resin fragmentation, or form bubble and low-densityization and embrittlement.By being adjusted to this state, make process of resin be processed into the form that is suitable for utilizing again easily.That is,, make and carry out easily as the after-treatments such as pelletizing, plastochondriaization, powderization and fragmentation of the regenerating resin of post processing because mechanical strength of resin descends.
The reason that can obtain such effect can be considered as follows.Owing in resin combination, have the diffusivity and the impregnability of height as the solvent of high-pressure fluid, therefore, after the fire retardant extraction is removed, still remain in the resin combination.This solvent discharges from resin under atmospheric pressure atmosphere gradually.At this moment, the hardness of control resin combination and the rate of release of solvent can make resin expanded.Though it is all applicable when used resin is thermosetting resin and thermoplastic resin that this foaming is handled,, therefore, be good to use thermoplastic resin because thermoplastic resin can be controlled its hardness by heating.
This foaming is handled can have following method particularly.But be not limited in these methods.
(1) extract to finish after, under the state to the resin softening temperature of in container, heating, high-pressure fluid is discharged from container.
(2) extraction is taken out resin after finishing from container, heats to more than the resin softening temperature.
(3) extraction is taken out resin after finishing from container, is decompressed to below the normal pressure under the state that is heated to more than the resin softening temperature.
The softening temperature of resin is meant glass transition temperature, softening temperature and the fusing point etc. of resin.
The following describes the formation of first kind of processing method of fire retardant resin composition of the present invention.
The fire retardant that can use in the present invention is halogen containing flame-retardant preferably.Be more preferably the addition type halogen containing flame-retardant.Because if fire retardant is an addition type, then extracts from resin easily and reclaim like this, therefore, use the halogen containing flame-retardant of the deterioration of easily being heated very effective.Its example has decabromodiphenyl, deca-BDE, tetrabromobisphenol A, tetrabromobisphenol A-two (2,3-dibromo propyl ether), tetrabromobisphenol A-two (allyl ether), hexabromo ring 12 carbon alkane, tribromphenol, tetrabromophthalic anhydride, two tetrabromo phthalimide, chlorinated paraffin wax and haloflex etc.
The example of other fire retardants has phosphonium flame retardant, contains nitrogen combustion inhibitor, siliceous fire retardant, antimony trioxide, aluminium hydroxide, boron compound etc., if additive flame retardant also can obtain same effect.Even reactive flame retardant is also applicable when the reactant molecule amount is low.
In the present invention, the resinous principle that constitutes fire retardant resin composition can be a thermoplastic resin, also can be thermosetting resin.The example of thermoplastic resin has polyethylene, polyolefin, polypropylene, polystyrene, PETG, polybutylene terephthalate (PBT), Merlon, nylon, polyvinyl chloride and acrylonitrile-butadiene-styrene copolymer etc.Can in above-mentioned fire retardant resin composition, add filler etc.
The example of thermosetting resin has thermosetting phenolic resin, thermosetting epoxy resin, thermosetting unsaturated polyester resin, polyurethane and Lauxite etc.At this moment, can be in fire retardant resin composition filling nonwoven or glass fibre etc., form composite.
The suitable example of used solvent is a carbon dioxide in high-pressure fluid of the present invention.Carbon dioxide has very high impregnability to resin, therefore easily diffuses to resin combination inside.And particularly when high-pressure fluid was in supercriticality, because impregnability improves, its extraction effect obtained performance.In addition, pressure of supercritical carbon dioxide (critical pressure) and temperature (critical-temperature) are respectively 7.38MPa and 31.1 ℃, and carbon dioxide promptly enters supercriticality in lower temperature, the diffusivity of performance height.And, can reduce the treatment temperature of extracting, have and suppress the be heated effect of deterioration of resin and fire retardant.In addition, in extracting treatment process,, therefore, need not to use big energy during processing owing to can remove fire retardant effectively at lower temperature.
As other solvents, also can make water and alcohol etc.When extracting antimony oxide and aluminium hydroxide etc., make water desirable good result.
In first kind of processing method of the present invention, the pressure of high-pressure fluid is preferably more than 1/2 times of critical pressure of solvent used in high-pressure fluid, below 5 times.The density of the solvent of high-pressure fluid increases near the critical pressure of this solvent greatly, and is corresponding therewith, and the solubility of solute increases, and thus, above-mentioned scope can be used as the pressure limit that can carry out preferable extraction of the present invention.Solubility in this pressure limit is tendency from about 1/2 times of increase of the critical pressure of solvent about 5 times.Wherein, considering from the angle of extraction effect and operability, is good with the pressure limit below 3 times to critical pressure more than the critical pressure of solvent.In the present invention, when making solvent, be preferably in the pressure limit of about 7.4PMa～about 22.2MPa and extract with carbon dioxide.
Yet, even, reactivity is also had effect, so also can adopt this condition not reaching the subcritical state of supercriticality.Though subcritical state does not have concrete definition, can be expressed as pressure critical pressure more than 1/2 and less than critical pressure, temperature critical-temperature more than 1/2 and less than the state of critical-temperature.
Be higher than room temperature and be lower than in 200 ℃ the scope extracting temperature, resin can carbonization, and halogen also is difficult for breaking away from from fire retardant.Therefore, the extraction of fire retardant, separation and recovering effect are good.In the present invention, owing to all purpose will be utilized as again, therefore, be preferably in 0～200 ℃ interior processing of scope with resin and fire retardant.Even but surpassing 200 ℃ temperature, the purpose of utilizing again according to resin may be more suitable condition sometimes.That is, in the scope more than 200 ℃, below 400 ℃,,, therefore, be suitable for situation about only resin being utilized again owing to the fire retardant dehalogenation occurring though can handle and not make its carbonization to resin in treatment temperature.And, can generate carbide by resin 400～600 ℃ temperature range, dehalogenation can take place in fire retardant, so when being suitable for only resin being utilized as carbide again.If temperature is high again, then the yield of carbide also descends, and therefore, is unfavorable for processing method of the present invention.
In addition, in the present invention, can add cosolvent at the solvent that is used for extracting.Except solvent, high-pressure fluid should contain above, the 50 moles of cosolvents that % is following of 1 mole of %.Preferably contain above, the 20 moles of cosolvents that % is following of 1 mole of %.This cosolvent constitutes high-pressure fluid with above-mentioned solvent, and its addition gets final product on a small quantity.This cosolvent that mixes can increase the compatibility of the fire retardant and the high-pressure fluid of extraction, improves the extraction efficiency of high-pressure fluid.When in first kind of processing method of the present invention, using halogen containing flame-retardant, with alcohols such as methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohols, hydro carbons such as hexane, propane, butane, cyclohexane, pentane, ketones such as acetone, ester classes such as ethyl acetate, methyl acetate, isoamyl acetate, or water etc. can be obtained very good effect as cosolvent.But, then be not limited to these cosolvents if can extract effectively.
In addition, in the present invention, in order from the resin combination that contains fire retardant, to extract fire retardant effectively, also can clean, the broken or pulverizing with fire retardant resin composition in advance.In addition, in order more effectively to handle, the above treatment temperature of softening temperature that is preferably in thermoplastic resin is carried out.Especially if resin can be handled at soft state or molten condition, then fire retardant resin composition can be supplied with extraction vessel continuously, extract processing continuously, and reclaim fire retardant and resin continuously.Second kind of processing method
The following describes second kind of processing method of fire retardant resin composition of the present invention, it comprises allows at least a portion of fire retardant resin composition of resinous and fire retardant contact with high-pressure fluid by solvent composition, reduces the operation of the anti-flammability of above-mentioned fire retardant resin composition.
For solving above-mentioned problem, in the processing method of second kind of fire retardant resin composition, remove flame-retardant composition from the resin combination that contains fire retardant, this method comprises allows the resin combination that contains halogen containing flame-retardant contact with high-pressure fluid, removes the dehalogenation operation of halogenic ingredient.In second kind of processing method, described " flame-retardant composition " be meant particularly fire retardant or with the chemically combined halogen element of resin combination composition.
For solving above-mentioned problem, in the processing method of second kind of fire retardant resin composition, from the resin combination that contains fire retardant, remove flame-retardant composition, it is characterized in that this method comprises allows the resin combination that contains halogen containing flame-retardant contact, to remove the dehalogenation operation of halogenic ingredient with high-pressure fluid and to handle the reduction operation of the resin combination of dehalogenation with the high-pressure fluid reduction.
In addition, for solving above-mentioned problem, in the processing method of flame-retarded resin of the present invention, from the resin combination that contains fire retardant, remove flame-retardant composition, the method is characterized in that, comprise the dehalogenation operation that allows the resin combination that contains halogen containing flame-retardant contact, remove halogenic ingredient with high-pressure fluid, handle the reduction operation of the resin combination of dehalogenation with the high-pressure fluid reduction, and the foamed process that the resin combination of above-mentioned dehalogenation is foamed and handles.
In above-mentioned foamed process, allow after the contacting of high-pressure fluid and dehalogenation, with solvent used in the above-mentioned high-pressure fluid processing of foaming, can reprocess expeditiously.
In addition, in second kind of processing method of fire retardant resin composition of the present invention,, can make the utilization again of the resin after the processing become easy by the abstraction process that non-halogen fire retardant is extracted, removes.
In above-mentioned dehalogenation operation, reduction operation or the foamed process of second kind of processing method of the present invention, when the treatment temperature of using high-pressure fluid is in 50～400 ℃ of scopes, can handle expeditiously.In addition, in above-mentioned dehalogenation operation, reduction operation or foamed process, when the pressure of high-pressure fluid is constituting in the scope below 3 times of more than 1/2 of critical pressure, critical pressure of the solvent of above-mentioned high-pressure fluid, can handle expeditiously.In addition, in above-mentioned dehalogenation operation, reduction operation, foamed process or abstraction process, when high-pressure fluid is, can handle expeditiously during as the solvent of principal component with carbon dioxide at least.
The halogen containing flame-retardant of applicable second kind of processing method of the present invention is brominated flame-retardant preferably.Applicable resin of the present invention is thermoplastic resin preferably.
Below be described more specifically second kind of processing method of the present invention.
According to the present invention, can from the resin combination that contains fire retardant, remove flame-retardant composition, thereby resin is utilized again.Removing on the basis of flame-retardant composition from the resin combination that contains fire retardant, the quality that has suppressed to be caused by hot deterioration etc. descends, thereby can utilize resin again.Removed flame-retardant composition, the quality that has suppressed to be caused by hot deterioration descends, thereby resin regeneration can be reprocessed into easy-to-use form simply.
The effect of used high-pressure fluid by solvent composition among the present invention at first, is described.The invention is characterized in, adopt solvent to make the high-pressure spray physical efficiency and remove flame-retardant composition expeditiously, and the solvent high-efficiency rate ground of use high-pressure fluid improves the quality of resinous principle.All kinds of solvents under high pressure has high density as fluid, and its effect is, and the solubility of solute is increased, the impregnability as the resin combination inside of object is improved and therefore reactivity also improves, or the like.Because it is big that reducing agent isoreactivity material is soaked into to the effect of resin combination inside, therefore, can improve the homogeneity and the yield of reaction.Especially the supercritical fluid more than the solvent critical point, temperature effect also increases, and kinetic energy increases, and effects raisings such as reactivity, dissolubility, impregnability and extractability.The present invention is exactly characteristics of utilizing this high-pressure fluid, and flame retardant resin is regenerated and utilized.
Below second kind of processing method of the present invention is described with Fig. 4～6.
Fig. 4 is the process chart of second kind of processing method of the present invention.In second kind of processing method of fire retardant resin composition of the present invention, for removing the flame-retardant composition halogen from the resin combination that contains halogen containing flame-retardant, make above-mentioned fire retardant resin composition contact high-pressure fluid, halogen is sloughed as halogen compounds such as hydrogen halides or halogenic molecules.Resin is sloughed halogen, modification (as forming the two keys of a part etc.) also can take place sometimes, but above-mentioned resin can not decompose and can utilize again.The halogen compounds that generates during as dehalogenation is as remaining in the treating apparatus, and therefore then halogen ionization and corrosion device etc. easily, separate it and reclaim.The halogen compounds purity that is recovered to is high more, also can directly utilize again.
At this moment, owing to use high-pressure fluid, the solvent of forming high-pressure fluid has very high diffusivity and impregnability in resin combination, therefore, can deeply carry out dehalogenation to resin combination inner, high efficiency ground.
Fig. 5 is another process chart of second kind of processing method of the present invention.In the processing method of fire retardant resin composition of the present invention, for from the resin combination that contains halogen containing flame-retardant, removing the flame-retardant composition halogen, allow above-mentioned fire retardant resin composition contact, halogen is sloughed as halogen compounds such as hydrogen halides or halogenic molecules with high-pressure fluid.Though resin does not decompose, sometimes because of dehalogenation partially modified (as forming two keys and crosslinked etc.).This modification part can cause resin variable color etc., the principal element that quality descends when becoming regeneration, thereby be unsuitable for the regeneration quality is had the utilization again of requirement.Therefore, ensuing processing is, the resin combination of dehalogenation is reduced processing, repairs the modification part, can obtain the good resin combination of quality thus.This reduction is handled by making through the resin combination of dehalogenation and is got final product with having added reducing agent, hydrogen or contacted through the high-pressure fluid that reaction can produce the reducing substanceses such as compound of hydrogen.Through handling like this, regenerating resin can be used for moulding again, utilizes again.
At this moment, as the use high-pressure fluid,, therefore, can deeply carry out dehalogenation and reduction processing to resin combination inner, high efficiency ground then because the diffusivity and the impregnability of solvent in resin of formation high-pressure fluid is big.
Following Fig. 6 is the another process chart of second kind of processing method of the present invention.Thereby the processing method of fire retardant resin composition of the present invention is to allow the high-pressure fluid contact contain the resin combination dehalogenation of halogen containing flame-retardant.Thereafter processing is, allows resin combination contact high-pressure fluid through dehalogenation, handles by reduction and repairs the modification part, and the quality of resin combination is improved.In addition, make resin combination contact high-pressure fluid, solvent-saturated is advanced among the resin combination.At this moment, the solvent of resin combination makes resin expanded by soaking into into.By this foamed process, the resin fragmentation, or form bubble, density reduces and embrittlement.Be suitable for carrying out the form of utilizing again of resin forming once again by being processed into this embrittlement state, can process of resin being processed into.That is,, therefore, can easily carry out after-treatments such as pelletizing, plastochondriaization, powderization and fragmentation as the regenerating resin of post processing because mechanical strength of resin reduces.
The reason that can obtain such effect is identical with the situation of above-mentioned first kind of processing method.
In addition, the foaming processing also can be identical with the situation of above-mentioned first kind of processing method.
Below specify the formation of second kind of processing method of fire retardant resin composition of the present invention.Though can under the condition substantially the same, carry out with above-mentioned first kind of processing method, because it is different to reduce the mechanism of anti-flammability, therefore, may not be identical.
Fire retardant in second kind of processing method is good with halogen containing flame-retardant, is good with widely used brominated flame-retardant especially.This is because brominated flame-retardant is to being that the aromatic resin of representative has good flame retardant effect with the styrene resin, and styrene resin is used in the various shells and the component materials of household appliances so far in a large number, therefore, can expect that these brominated flame-retardants have the huge effect that can handle a large amount of styrene resin composites.The example of brominated flame-retardant has diphenyl ether fire retardants such as deca-BDE, octabromodiphenyl ether, tetrabromodiphenyl ether, tetrabromobisphenol A bisphenol-A based flame retardants such as (TBA), brominated flame-retardants such as hexabromo ring 12 carbon alkane, two (tribromophenoxy) ethane, tribromphenol, ethylenebis (tetrabromo phthalimide), tetrabromophthalic anhydride, two tetrabromo phthalimide, TBA polycarbonate oligomer, brominated Polystyrene, TBA epoxy oligomer.As chlorine-containing flame retardant, also can enumerate chlorinated paraffin wax, haloflex, perchloro-ring pentadecane, chlorendic acid etc.
Other fire retardants have phosphonium flame retardant, contain nitrogen combustion inhibitor, siliceous fire retardant, antimony trioxide, aluminium hydroxide, boron compound etc.According to the kind of the resin that is added and purposes etc., they can use separately, also can merge use, and its content is adjusted according to purposes.
Resin applicable to second kind of processing method of the present invention is identical with the situation of above-mentioned first kind of processing method.Fire retardant resin composition can contain additives such as flame retardant, stabilizing agent, colouring agent, flow ability modifying agent and releasing agent.
The used solvent of second kind of processing method of the present invention can be various organic solvents such as alcohol etc., but preferably carbon dioxide and water.
Carbon dioxide has high impregnability to resin, is diffused into resin combination inside easily.And as using high-pressure fluid in supercriticality, then impregnability further improves, and thus, can bring into play good extraction effect, also can expect, the reactivity of resin combination inside also further improves.About being suitable in each operation of processing method, carbon dioxide is applicable to the arbitrary operation in dehalogenation operation, reduction operation, foamed process and the abstraction process.Particularly, then, need not to remove the drying process that desolvates after the processing, handle engineering and can simplify owing to be gas if in final treatment process, use carbon dioxide.In addition, carbon dioxide is respectively 7.38MPa and 31.1 ℃ in the pressure (critical pressure) of supercriticality and temperature (critical-temperature), and more than the critical point, carbon dioxide just becomes supercriticality at this.Like this, carbon dioxide promptly enters supercriticality and has the diffusivity of height at low temperature, therefore, can implement high efficiency processing at low temperature, does not need big energy.
When the temperature and pressure of water rose, its diffusivity and impregnability improved, and, increase and the oxidation catalysis that produces and character such as water-disintegrable strengthen by ionic product.When effectively utilizing these character, Jiang Shui to be used for second kind of processing method, can be used for dehalogenation operation, reduction operation, foamed process and abstraction process.Especially effective in dehalogenation operation of reacting and reduction operation.Water is respectively 22.1MPa and 374.1 ℃ in the pressure (critical pressure) of supercriticality and temperature (critical-temperature), more than the critical point, just becomes supercriticality at this.Yet, even do not reach the subcritical state of supercriticality, also can obtain effect to reactivity, therefore, also can under this condition, use.Though subcritical state does not have concrete definition, can be expressed as pressure critical pressure more than 1/2 and less than critical pressure, temperature critical-temperature more than 1/2 and less than the state of critical-temperature.
High-pressure fluid in second kind of processing method according to and above-mentioned first kind of reason that processing method is same, except solvent, also can contain cosolvent.Cosolvent content is at 1 mole more than the %, 50 moles below the % preferably, be preferably in 1 mole of % above, 20 moles below the %.When being especially in use in halogen containing flame-retardant, cosolvent can be to reduce reducing substanceses such as the hydrogen handled, carbon monoxide, alcohols such as methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, hydro carbons such as hexane, propane, butane, cyclohexane, pentane, ketones such as acetone etc., they can use separately, use also capable of being combined.
The pressure of the high-pressure fluid that in each operation of second kind of processing method of the present invention, uses should be in high-pressure fluid used solvent more than 1/2 times of critical pressure, below 3 times.The density of the solvent of high-pressure fluid increases near the critical pressure of this solvent greatly, and is corresponding therewith, and the solubility of solute increases, and thus, above-mentioned scope can be used as the pressure limit that can carry out preferable extraction of the present invention.Solubility is from about 1/2 times of increase of solvent critical pressure, the tendency that the state of reaching capacity is arranged in the time of about 3～5 times, but consider solvent more than the critical pressure to critical pressure below 3 times the time solvent to the impregnability height of resin inside, and consider operability, therefore, above-mentioned scope can be used as preferable pressure limit.
Though the temperature upper limit of used high-pressure fluid is looked resin and different in each operation of the present invention, the temperature of used high-pressure fluid is room temperature preferably, or is in the temperature range more than 50 ℃, below 400 ℃ better.In this temperature range, resin can carbonization in each treatment process, and can make the fire retardant dehalogenation.In addition, in reduction operation and foamed process etc., the situation that also less generation regenerating resin quality descends, therefore above-mentioned scope is preferable.And, when making the fire retardant dehalogenation, can generate carbide by resin 400～600 ℃ temperature range, therefore be fit to the situation that resin is utilized as carbide again.
Below each operation such as the dehalogenation operation in second kind of processing method of the present invention, reduction operation, foamed process and abstraction process is described.
In the dehalogenation operation of second kind of processing method of the present invention, the halogen of halogen containing flame-retardant contained in the fire retardant resin composition is broken away from, removes.Knownly halogen is sloughed the fire retardant resin composition heating and produced hydrogen halides.Therefore, the dehalogenation reaction can be undertaken by heating.During heat treated, the temperature that makes high-pressure fluid is more than 100 ℃, is preferably 200～400 ℃ and carries out dehalogenation.At this moment, because the high-pressure spray physical efficiency is soaked into effectively to resin combination inside, therefore, can carry out dehalogenation efficiently.Additive method has from the method for the outside irradiation of reaction vessel, promotion dehalogenation.In addition, dehalogenation operation and reduction treatment process are carried out simultaneously, carry out dehalogenation and reduction thus simultaneously.Utilize this law also can carry out dehalogenation, can handle room temperature (being preferably in more than 50 ℃) at low temperature.
Then, the reduction operation is carried out under the state under reducing substances and the high-pressure fluid coexistence.Particularly, can repair the unsaturated double-bond that produces by the fire retardant dehalogenation, the quality of regenerating resin is improved by hydrogenation.Allow dehalogenation and reduction when carrying out simultaneously above-mentioned, can obtain can not generating unsaturated double-bond because of dehydrohalogenation with the regenerating resin of original resin same quality.The hydrogenation of reduction operation is owing to carry out in high-pressure fluid, so its reactive height can make reducing substances such as hydrogen arrive resin inside expeditiously.
In the present invention, be impregnated into resin combination inside, reduce processing expeditiously for making high-pressure fluid, available following method is supplied with hydrogen:
(1) import hydrogen,
(2) import carbon monoxide, described carbon monoxide with the situation of water coexistence under convert hydrogen to by water gas shift reaction,
(3) import hydrocarbon compound, be used for when oxygen exists, generating hydrogen through water gas shift reaction by the carbon monoxide that generates by partial oxidation,
(4) importing tetrahydronaphthalene, oil are heavy oil, edible wet goods hydrogen supply dissolvent.
For the hydrogenation that promotes that they cause, also can use hydrogenation catalyst commonly used and hydrogenolysis catalyst etc., as copper catalyst, Raney nickel, cupric oxide, iron oxide, drape over one's shoulders palladium catalyst etc.The temperature of the high-pressure fluid that uses during reduction is handled is room temperature～200 ℃ when using catalyst, can be room temperature～400 ℃ during without catalyst.
The foamed process of second kind of processing method of the present invention by utilize above-mentioned high-pressure fluid to the height impregnability of resin, allow above-mentioned high-pressure fluid impregnated with resin and it is sharply discharged carry out.The effect of this foaming operation is higher when resin is softening, so easily be applied to the thermoplastic resin composition.Treatment temperature is better with 50～300 ℃ scope.The solvent-saturated that can make high-pressure fluid in any operation in above-mentioned dehalogenation operation and the reduction operation is carried out foamed process after these operations in resin.
Abstraction process in second kind of processing method of the present invention is also effective when fire retardant resin composition also contains fire retardant beyond the halogen containing flame-retardant.That is, when removing the non-halogen containing flame-retardant of addition type such as antimony trioxide, can handle by the extraction of high-pressure fluid and be removed effectively.At this moment, also can utilize the specialities such as dissolubility, impregnability of high-pressure fluid, deeply to the resin inner, high efficiency removed.By this processing, the quality of the resin that can make regenerates handled improves.In addition, this abstraction process need not to separate with above-mentioned other operation and carries out, and can carry out extracting in this processing with high-pressure fluid in the arbitrary operation in dehalogenation operation, reduction operation and the foamed process.
Each operation of the present invention can be implemented successively.Also can carry out series of processes simultaneously.Thus, can improve treatment effeciency.
In addition, in the present invention, for handling the resin combination that contains fire retardant expeditiously, also can clean, the broken and pulverizing with pending resin combination in advance.
Can keep high-pressure fluid as long as be used for the device of the present invention's processing, be not particularly limited.Wherein, be the corrosion of the halogen compounds avoiding sloughing, preferably use container and the pipeline made by the nichrome in the corrosion resistant nickel alloy or Hastelloy, titanium, titanium alloy etc. container and pipeline etc.When carrying out the neutralisation treatment etc. of halogen compounds at the same time, the container that can use widely used stainless steel etc. to make reclaims when waiting separating, and can be only uses the container that be made by the corrosion resistance material etc. in the part that may have halogen compounds.Like this, can reduce equipment investment.
Below with embodiment the processing method of fire retardant resin composition of the present invention is made more specific description, but the present invention is not limited in these embodiment.In embodiment 1 to 5, implement first kind of processing method, in embodiment 6 to 10, implement second kind of processing method.
Embodiment 1
Plate body (big or small 3cm * the 3cm of being that will contain the polystyrene resin composite of the about 10 weight % of fire retardant deca-BDE, thick 1mm) 5g puts into the high pressure extraction container that volume is 0.1L, make high-pressure fluid (solvent) with 50 ℃, the supercritical carbon dioxide of 10MPa, extract fire retardant.To extract solvent and send in the gas-liquid separation container, reclaim fire retardant, the residual plate body of having removed the polystyrene resin composite of fire retardant in the high pressure extraction container.After about 5 hours of extraction time, the recovery of fire retardant finishes substantially.
About 98% of fire retardant in the resin combination is removed through extraction, and about 95% fire retardant is reclaimed by separation container.The purity of the fire retardant that this is recycled to is decomposed deterioration seldom about 98%.
Billet (big or small 10cm * the 0.5cm of being that will contain the phenolic cured resin composition of the about 10 weight % of fire retardant tribromphenol, thick 1mm) 5g puts into the high pressure extraction container that volume is 0.1L, makes the solvent extraction fire retardant with 80 ℃, the supercritical carbon dioxide of 15MPa.To extract solvent and send in the gas-liquid separation container, and reclaim fire retardant, the billet of having removed the phenolic cured resin composition of fire retardant remains in the high pressure extraction container.The recovery of fire retardant finishes substantially through about 5 hours extraction.
About being extracted more than 95% of the fire retardant in the resin combination removed, and about 95% fire retardant is reclaimed by separation container.The purity of the fire retardant that this is recycled to is decomposed deterioration seldom about 98%.
With treated phenolic cured resin composition carbonization treatment in the gas retort device, can make active carbon, but be substantially devoid of the bromine composition in the gas of at this moment discharging.According to above-mentioned situation, can expect, adopt first kind of processing method of the present invention can suppress to constitute the deterioration of the resin of gas retort.
Embodiment 3
Plate body (size is 3cm * 3cm, the thick 1mm) 50g that will contain the polystyrene resin composite of the about 10 weight % of fire retardant deca-BDE puts into the autoclave that volume is 1L, and at 20 ℃, the liquid carbon dioxide that is about 5.7MPa with vapour pressure extracts fire retardant.Adopt batch process, extracted 1 hour, reclaim fire retardant, repeat 5 times.
About fire retardant more than 95% in the resin combination can be extracted.At this moment, the fire retardant that is recovered to has 99% purity, can reclaim fire retardant to decompose the few state of deterioration.The resin that is recovered to can be made granularly, be used for moulding again, gained particle only mechanical strength slightly descends, and can utilize fully again.
Embodiment 4
Similarly to Example 1, extract fire retardant from fire retardant resin composition, different is to add 5% the hexane as cosolvent in the extraction solvent of high-pressure fluid.Can in about 3 hours, finish basically with the extraction of embodiment 1 equal extent and reclaim, confirm to add the organic efficiency that cosolvent has improved fire retardant.Resin that is recovered to and fire retardant have the quality with embodiment 1 cardinal principle same degree.
Thin slice (thick 0.2mm) 2g of pet resin composition that will contain the fire retardant deca-BDE of the 5 weight % that have an appointment puts into the high pressure extraction container that volume is 0.1L, make solvent with 60 ℃, the supercritical carbon dioxide of 10MPa, extract fire retardant, to extract solvent and send into the gas-liquid separation container, reclaim fire retardant, the pet resin composition thin slice of having removed fire retardant remains in the high pressure extraction container.Extracted through 5 hours approximately, the recovery of fire retardant finishes substantially.
After being cooled to room temperature, take out thin slice, put into immediately and be adjusted to 100 ℃ heating furnace.The carbon dioxide that is contained in the thin slice under this state sharply gasifies, and constitutes soft state resin expanded of thin slice.The bubble of thin slice is more than tens of microns, and intensity descends and embrittlement.Thin slice before extracting, and with its pulverizing, easier being cut off, the thin slice of this embrittlement is then pulverized easily, easily with its pulverize resin for utilizing again.
Acrylonitrile-butadiene-styrene (ABS) copolymer resins (the ABS resin that will contain the about 5 weight % of fire retardant tetrabromobisphenol A (TBA), weight average molecular weight 30000,220 ℃ of heat distortion temperatures) (size is 3cm * 3cm to the plate body of composition, thick 1mm) 5g puts into the high-pressure bottle that volume is 0.1L, makes solvent with 350 ℃, the supercritical carbon dioxide of 15MPa and fire retardant is carried out debrominate handles (dehalogenation).After this processing, release pressure reclaims resin combination, and is positioned under the room temperature atmosphere, because the carbon dioxide that residues in the resin combination is slowly overflowed, need not to carry out drying.
Carry out because the debrominate processing is the temperature more than heat distortion temperature, therefore, resin combination composition deformation and fusion after the processing become block.Bromine composition in the parsing tree oil/fat composition finds that about bromine composition more than 99% is removed, weight average molecular weight no significant change before and after handling.In addition, though resin combination changes because of engaging vibrating bromize hydrogen, mouldability no change before and after handling uses so the resin combination after handling can be used as regenerating resin fully.
Embodiment 7
Polystyrene resin (the weight average molecular weight 35000 that will contain the about 5 weight % of fire retardant tribromphenol, 82 ℃ of heat distortion temperatures) (size is 3cm * 3cm to the plate body of composition, thick 1mm) 5g puts into the high-pressure bottle that volume is 0.1L, fire retardant is carried out debrominate handle with 250 ℃, the water as solvent of the subcritical state of 20MPa., keep-up pressure with temperature-resistant, send into hydrogen, make temperature rise to 300 ℃ thereafter.Then, make temperature drop to 100 ℃, pressure is reduced to normal pressure gradually, make temperature reduce to room temperature then, reclaim resin combination.After this operation, the resin combination that is recovered to need not further drying.
Carry out because processing is the temperature more than heat distortion temperature, therefore, resin combination composition deformation and fusion after the processing become block.Bromine composition in the parsing tree oil/fat composition finds that about bromine composition more than 99% is removed, and the weight average molecular weight after the processing descends to some extent than before handling.Yet, variable color does not take place basically, and the mouldability before and after handling do not see difference, hence one can see that, and the resin after the processing can be used as regenerating resin fully and uses.
Polystyrene resin (the weight average molecular weight 35000 that will contain the about 5 weight % of fire retardant tribromphenol, 82 ℃ of heat distortion temperatures) (size is 3cm * 3cm to the plate body of composition, thick 1mm) 5g and Raney nickel 0.1g put into the high-pressure bottle that volume is 0.1L, supply is mixed the cosolvent carbon monoxide of 3 moles of % and the high-pressure fluid that obtains in 180 ℃, the water of the subcritical state of 20MPa, carry out the debrominate of fire retardant and handle.Thereafter, allow temperature reduce to 100 ℃, pressure is reduced to normal pressure gradually, allows temperature reduce to room temperature again, reclaims resin combination.After this operation, the resin combination that is recovered to needn't be gone dry again.The resin combination that is recovered to is identical with embodiment 7 outward appearances, and the bromine composition in the resin combination is removed basically, and the weight average molecular weight after the processing descends to some extent than before handling, but the resin combination after handling has the quality that can be used as the regenerating resin use fully.
High impact polystyrene resin (the HIPS that will contain the about 5 weight % of fire retardant tetrabromobisphenol A (TBA), weight average molecular weight 36000,76 ℃ of heat distortion temperatures) (size is 3cm * 3cm to the plate body of composition, thick 1mm) 5g and hydrogen supply cosolvent tetrahydronaphthalene 5g put into the high-pressure bottle that volume is 0.1L, handle as debrominate and reduction that solvent carries out fire retardant with 300 ℃, the supercritical carbon dioxide of 15MPa.
Carry out after these handle, resin combination is cooled to 40 ℃ below the thermal transition temperature of resin again, release pressure reclaims resin combination, immediately resin combination is put into the decompression heating furnace that is adjusted to 150 ℃.Through this processing, the carbon dioxide that is contained in the resin combination sharply gasifies, the resin combination foaming of soft state.Observe the cross section of the resin combination of foaming, the bubble size in the discovery resin combination is about tens of microns, and intensity descends and embrittlement.
Bromine composition in the parsing tree oil/fat composition finds that about bromine composition more than 99% is removed, and the weight average molecular weight after the processing descends to some extent than before handling.Yet, do not have variable color basically.During with the resin combination moulding once again after the foaming, and broken easily, the moulding resin raw material that can be used as powdery is regenerated owing to embrittlement for it.
Polystyrene resin (the weight average molecular weight 35000 that will contain about 5 weight % of fire retardant tribromphenol and antimony trioxide 2 weight %, 82 ℃ of heat distortion temperatures) (size is 3cm * 3cm to the plate body of composition, thick 1mm) 5g puts into the high-pressure bottle that volume is 0.1L, supply is mixed the high-pressure fluid that 3 moles of % cosolvent carbon monoxide form in 250 ℃, the water of the subcritical state of 20MPa, carry out the debrominate of fire retardant and handle.In this processing, high-pressure fluid descends by heat exchanger, is admitted in the flow separation container, is separated into gas componant and solid-liquid composition.Moisture in the gas componant, hydrogen, carbon monoxide, carbon dioxide and hydrogen bromide, trioxygen-containing antimony, water and think the material of the some additives in the resin combination in the solid-liquid composition.
Resin combination that is recovered to and embodiment 7 have same outward appearance, and the bromine composition in the resin combination is removed basically, and antimony trioxide also reduces.Can think that thus brominated flame-retardant is dehalogenation, antimony trioxide is extracted out.The gained resin combination though the weight average molecular weight after it is handled descends to some extent than before handling, has the quality that can be used as the regenerating resin use fully.
The foregoing description shows, uses first processing method of fire retardant resin composition of the present invention, extracts fire retardant with high-pressure fluid from the resin combination that contains fire retardant, can obtain following good result.
That is, can they be reclaimed, and they can be utilized as good regenerated resources again with the state that resinous principle and fire retardant deterioration and quality are descended.
When using thermoplastic resin, in extract handle after, used solvent makes resin expanded and embrittlement when extracting, and the granulation and the efflorescence of the resin after the processing are become easily, easily it is handled when resin is utilized again.
When using the thermosetting resin be difficult to usually to regenerate, can easily utilize again material by removing cosolvent.For example, when the carbide to thermosetting resin carries out Reuse of materials, in the carbonization treatment operation, can not produce hydrogen halides etc. because of dehalogenation.Therefore, the material of making treating apparatus needs not to be the special material of halogen resistant, available inexpensive common used material.And, also can reduce the investment of exhaust gas treatment device and load.
The dehalogenation not because flame-retardant composition is extracted with the original form of fire retardant, therefore, the material of making the fire retardant resin composition treating apparatus can be common used materials such as stainless steel commonly used in high-pressure bottle and the pipeline etc., and needn't be with the special material of the costliness with halogen resistant.
When resin is used as the reducing agent of the iron ore in the blast furnace and coke oven raw material,, therefore, can utilize again under the state of pipeline deterioration etc. needn't worrying also because can obtain can not producing the resin of hydrogen halides etc. by removing fire retardant in advance.
On the other hand, the foregoing description shows, second kind of processing method of fire retardant resin composition of the present invention contacts, carries out the operation of dehalogenation with high-pressure fluid based on the resin combination that will contain halogen containing flame-retardant, resinous principle is decomposed and recycling resin, and had following good result.
That is, handle by dehalogenation, the resin combination of the flame-retardant composition that can be removed, and recyclable quality descend little, can be used as the resinous principle that good regenerated resources are utilized again.
Fire retardant resin composition is carried out dehalogenation handle, and reduce processing again, can make the regeneration such as unsaturated bond that generate by dehalogenation.And, can reclaim the resinous principle that quality decline is little, can be used as good renewable resource utilization.
When using thermoplastic resin, after processing is handled and reduced to dehalogenation, the solvent of available high-pressure fluid makes resin combination foaming and the embrittlement that contacts with high-pressure fluid, makes easy pelletizing of resin and efflorescence after the processing, when resin is utilized again easily to its processing.
To remove because of the flame-retardant composition that contains in the resin combination that fire retardant is difficult to utilize usually again, just carry out Reuse of materials easily.
Utilize the high impregnability of high-pressure fluid, can deeply carry out the high efficiency processing of homogeneous to resin combination inside.
With Atmospheric components carbon dioxide or water solvent as high-pressure fluid, though handle the back do not carry out solvent seasoning also can the reclaiming resin.
As mentioned above, the present invention has huge industrial value.
Claims (13)
1. the processing method of fire retardant resin composition, it is characterized in that it comprises the operation that at least a portion of the fire retardant resin composition of resinous and fire retardant and the highly pressurised liquid by solvent composition is contacted, makes the anti-flammability reduction of above-mentioned fire retardant resin composition.
2. the processing method of fire retardant resin composition as claimed in claim 1, it is characterized in that, contact, above-mentioned fire retardant is extracted the anti-flammability that reduces above-mentioned fire retardant resin composition with highly pressurised liquid by at least a portion that makes above-mentioned fire retardant resin composition.
3. the processing method of fire retardant resin composition as claimed in claim 2 is characterized in that, it comprises the operation that will extract the above-mentioned fire retardant resin composition foaming behind the above-mentioned fire retardant with the solvent that constitutes above-mentioned high-pressure fluid.
4. the processing method of fire retardant resin composition as claimed in claim 2 is characterized in that, above-mentioned solvent is a carbon dioxide.
5. the processing method of fire retardant resin composition as claimed in claim 2 is characterized in that, above-mentioned high-pressure fluid contains cosolvent.
6. the processing method of fire retardant resin composition as claimed in claim 2 is characterized in that, the pressure of above-mentioned high-pressure fluid is more than the critical pressure of the solvent that constitutes above-mentioned high-pressure fluid, and at below 3 times of above-mentioned critical pressure.
7. the processing method of fire retardant resin composition as claimed in claim 2 is characterized in that, the pressure of above-mentioned high-pressure fluid is in more than 1/2 of critical pressure of the solvent that constitutes above-mentioned high-pressure fluid, and below above-mentioned critical pressure.
8. the processing method of fire retardant resin composition as claimed in claim 1, it is characterized in that above-mentioned fire retardant is a halogen containing flame-retardant, at least a portion of above-mentioned fire retardant resin composition is contacted with high-pressure fluid, slough the halogen in the above-mentioned fire retardant resin composition, reduce its anti-flammability.
9. the processing method of fire retardant resin composition as claimed in claim 8 is characterized in that, it comprises the operation that makes the above-mentioned fire retardant resin composition reduction behind the dehalogenation with the solvent that constitutes above-mentioned high-pressure fluid.
10. the processing method of fire retardant resin composition as claimed in claim 9 is characterized in that, it also comprises the operation that makes the above-mentioned fire retardant resin composition foaming behind the dehalogenation with the solvent that constitutes above-mentioned high-pressure fluid.
11. the processing method of fire retardant resin composition as claimed in claim 8 is characterized in that, above-mentioned solvent is a carbon dioxide.
12. the processing method of fire retardant resin composition as claimed in claim 8 is characterized in that, the pressure of above-mentioned high-pressure fluid is more than the critical pressure of the solvent that constitutes above-mentioned high-pressure fluid, and at below 3 times of above-mentioned critical pressure.
13. the processing method of fire retardant resin composition as claimed in claim 8, the pressure that it is characterized in that above-mentioned high-pressure fluid be in more than 1/2 of critical pressure of the solvent that constitutes above-mentioned high-pressure fluid, and below above-mentioned critical pressure.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP146541/2000 | 2000-05-18 | ||
| JP2000146541A JP2001323105A (en) | 2000-05-18 | 2000-05-18 | Method for treating flame-retardant resin |
| JP2000146539A JP2001323103A (en) | 2000-05-18 | 2000-05-18 | Treating method for flame-retardant resin |
| JP146539/2000 | 2000-05-18 |
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| Publication Number | Publication Date |
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| CN1324716A true CN1324716A (en) | 2001-12-05 |
| CN1197694C CN1197694C (en) | 2005-04-20 |
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| CNB01116994XA Expired - Fee Related CN1197694C (en) | 2000-05-18 | 2001-05-18 | Method for treatment of fire retardant resin composition |
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| US10465058B2 (en) | 2016-12-20 | 2019-11-05 | The Procter & Gamble Company | Method for purifying reclaimed polymers |
| US10450436B2 (en) | 2016-12-20 | 2019-10-22 | The Procter & Gamble Company | Method for purifying reclaimed polypropylene |
| US11008433B2 (en) | 2018-06-20 | 2021-05-18 | The Procter & Gamble Company | Method for separating and purifying polymers from reclaimed product |
| US10941269B2 (en) | 2018-06-20 | 2021-03-09 | The Procter & Gamble Company | Method for purifying reclaimed polyethylene |
| US10899906B2 (en) | 2018-06-20 | 2021-01-26 | The Procter & Gamble Company | Method for purifying reclaimed polypropylene |
| US10961366B2 (en) | 2018-06-20 | 2021-03-30 | The Procter & Gamble Company | Method for purifying reclaimed polymers |
| WO2022090754A1 (en) * | 2020-10-30 | 2022-05-05 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Method and device for extracting additives from plastic-based material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2611207B1 (en) * | 1987-02-19 | 1989-07-13 | Rhone Poulenc Sante | PROCESS FOR THE PURIFICATION OF STYRENE COPOLYMERS WITH VINYLPYRIDINES BY EXTRACTION USING SUPERCRITICAL GAS |
| NZ246440A (en) * | 1991-12-18 | 1996-01-26 | Schering Corp | Process for cleaning vulcanized elastomeric articles using at least one supercritical fluid, purified articles produced thereby |
| CN1067411C (en) * | 1993-10-29 | 2001-06-20 | 纳幕尔杜邦公司 | Solution of perfluorinated polymers in supercritical CO2 |
| US5696195A (en) * | 1996-06-04 | 1997-12-09 | E. I. Du Pont De Nemours And Company | Solutions of perfluorinated polymers in SF6 with or without CO2 |
| US5756657A (en) * | 1996-06-26 | 1998-05-26 | University Of Massachusetts Lowell | Method of cleaning plastics using super and subcritical media |
| JP3311291B2 (en) | 1997-08-13 | 2002-08-05 | 川崎製鉄株式会社 | Plastic processing equipment |
| JPH11140223A (en) | 1997-11-07 | 1999-05-25 | Hitachi Ltd | Treatment of halogen-containing plastic and apparatus therefor |
| JP3816218B2 (en) | 1997-11-26 | 2006-08-30 | オルガノ株式会社 | Method and apparatus for decomposing organic compounds containing halogen atoms and / or sulfur atoms |
| JP2998734B2 (en) | 1998-02-09 | 2000-01-11 | 日本電気株式会社 | Recovery method of inorganic substances using supercritical water |
-
2001
- 2001-05-16 US US09/858,681 patent/US6429284B2/en not_active Expired - Fee Related
- 2001-05-18 CN CNB01116994XA patent/CN1197694C/en not_active Expired - Fee Related
-
2002
- 2002-06-19 US US10/174,638 patent/US20030018161A1/en not_active Abandoned
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107709427A (en) * | 2015-06-30 | 2018-02-16 | 宝洁公司 | Method for purifying contaminated polyethylene |
| CN107709427B (en) * | 2015-06-30 | 2020-11-17 | 宝洁公司 | Process for purifying contaminated polyethylene |
Also Published As
| Publication number | Publication date |
|---|---|
| US20010044520A1 (en) | 2001-11-22 |
| US6429284B2 (en) | 2002-08-06 |
| CN1197694C (en) | 2005-04-20 |
| US20030018161A1 (en) | 2003-01-23 |
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